WO2004089963A1 - Compositions and methods for facilitating reaction at room temperature - Google Patents
Compositions and methods for facilitating reaction at room temperature Download PDFInfo
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- WO2004089963A1 WO2004089963A1 PCT/US2004/010280 US2004010280W WO2004089963A1 WO 2004089963 A1 WO2004089963 A1 WO 2004089963A1 US 2004010280 W US2004010280 W US 2004010280W WO 2004089963 A1 WO2004089963 A1 WO 2004089963A1
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- reactant
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- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- NCCHARWOCKOHIH-UHFFFAOYSA-N n-methylbenzamide Chemical compound CNC(=O)C1=CC=CC=C1 NCCHARWOCKOHIH-UHFFFAOYSA-N 0.000 description 1
- OLLZXQIFCRIRMH-UHFFFAOYSA-N n-methylbutanamide Chemical compound CCCC(=O)NC OLLZXQIFCRIRMH-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- QJQAMHYHNCADNR-UHFFFAOYSA-N n-methylpropanamide Chemical compound CCC(=O)NC QJQAMHYHNCADNR-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- IFJPRZVRUSJPOC-UHFFFAOYSA-N non-1-yne;hydrate Chemical compound O.CCCCCCCC#C IFJPRZVRUSJPOC-UHFFFAOYSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- SGLDQLCVBBVVAJ-UHFFFAOYSA-N prop-2-enamide;sulfuric acid Chemical compound NC(=O)C=C.OS(O)(=O)=O SGLDQLCVBBVVAJ-UHFFFAOYSA-N 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- 125000000464 thioxo group Chemical group S=* 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- SWUFZSQHKFLQTM-UHFFFAOYSA-N tripyrazol-1-yl borate Chemical class C1=CC=NN1OB(ON1N=CC=C1)ON1C=CC=N1 SWUFZSQHKFLQTM-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/28—Compounds containing heavy metals
- A61K31/282—Platinum compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
Definitions
- the present invention relates to compounds or ligands, and compositions and methods utilizing such compounds. More particularly, the invention relates to ligands including first and second heteroatoms, transition metal complexes of such ligands, and methods of using the ligands and complexes, for example, to facilitate or promote chemical reactions, such as hydration of nitriles, and terminal alkynes and alkenes, and the hydrolysis of amides and the like .
- Medicinal chemists and biochemists want to know how amino acids are arranged in proteins, so that they can better understand the correlation between structures and the functions of drugs.
- One of the techniques used to accomplish the task of protein structure determination requires the breaking of amide bonds to liberate the amino acids.
- organisms found in nature have remarkably efficient systems to make and break amide bonds.
- Engineers have used natural enzymes such as carboxypeptidase to do the task of amide bond cleavage.
- amide bond cleavage involves proton transfer between imidazole, a carboxylate, and the amide undergoing hydrolysis
- other enzymatic systems involve a metal-catalyzed amide bond cleavage such as that seen in the zinc (II) -metalloprotease .
- existing enzymatic systems can be very complicated and sometimes difficult to handle due to their sensitivity to temperature and pH.
- Amide hydrolysis has been catalyzed not only by enzymes, but also by acids, bases, and metal ions. These systems take advantage of one or more possible factors, which facilitate amide bond cleavage.
- the amide bond cleaving reagent or catalyst could act as a proton transfer reagent, which can be an important factor in amide bond hydrolysis.
- a metal may catalyze or mediate amide hydrolysis by acting as a Lewis acid through O-complexation, delivery of a metal-coordinated hydroxide or a combination of the latter two processes.
- nitrile hydration is shown by the industrial hydrolysis of acrylonitrile, which is used to make acrylic acid which, in turn, can be converted to a variety of esters such as methyl, ethyl, butyl, and 2-ethylhexyl acrylates.
- the acrylates can then be used as co-monomers with methyl methacrylate and/or vinyl acetate to give polymers for water-based paints, among other products.
- this synthetic route involves the use of a stoichiometric amount of sulfuric acid to produce the acrylamide sulfate, which is then treated with an alcohol to give the acrylic ester. It would be advantageous to provide a direct route from the acrylonitrile and alcohol to yield the desired acrylate without the need to use and then neutralize a strong acid by using, for example, an efficient reaction facilitator, e.g., a catalyst.
- An example of an environmentally desirable method of conducting organic synthesis involves the addition reactions of water or amines to unsaturated hydrocarbons. For example, the metal-catalyzed hydration of alkynes is an important route to carbonyl compounds . The use of water in such syntheses has the additional advantages of ease of use, safety, and economic savings.
- reaction facilitators e.g., catalysts, promoters and the like, that mimic enzymatic systems in their hydrogen-bonding and/or proton transfer abilities, and are robust, simple to handle, easily produced and operate efficiently at room temperature .
- transition metal complexes including such ligands and methods for using the ligands and complexes have been discovered.
- the present ligands and transition metal complexes can be produced using relatively straightforward synthetic chemistry techniques.
- the structures of the present ligands and metal complexes can be effectively selected or even controlled, for example, in terms of proton transfer ability and/or hydrogen bonding ability, thereby providing ligands and complexes with properties effective to facilitate one or more chemical reactions.
- the present metal complexes can be effectively used to facilitate, for example, catalyze, promote, and the like, various chemical reactions, such as hydrolysis, alcoholysis, aminolysis, carbon dioxide conversion, hydroamination and hydration reactions.
- compositions which comprise at least one organic ligand and a transition metal partially complexed by the organic ligand.
- the present organic ligands include a first heteroatom and a second heteroatom.
- the first and second heteroatoms may be covalently bonded to each other or, in a preferred embodiment, are separated one from the other by at least one atom, for example, a carbon atom.
- one or both of the first and second heteroatoms may be covalently bonded to the transition metal.
- each of the first and second heteroatoms presents a lone pair of electrons that can be free (unbonded) , protonated, occasionally or temporarily bonded to an aforementioned transition metal, e.g., through a coordinate covalent bond, or hydrogen bonded to a second molecule, e.g., water.
- This variability in functionality affords the desired cooperativity sought in a ligand of the invention, especially whenever catalytic activity is desired.
- R 1 is t-butyl.
- X is a heteroatom which may be, for example, a nitrogen atom (N) , an oxygen atom (0) , or a sulfur atom (S) .
- X is a phosphorus atom (P) .
- the present organic ligands can be very effectively structured and adapted to control the proton transfer ability and/or hydrogen bonding ability of the transition metal complex of which the ligand is a part.
- the present ligands can be selected to obtain the desired degree of proton transfer ability and/or hydrogen bonding ability so that the resulting transition metal complex is highly effective in performing a desired chemical transformation, for example, hydrolysis, alcoholysis, aminolysis, carbon dioxide conversion, and addition of water, alcohols, ammonia or amines to alkenes and alkynes.
- Such reactions are typically performed by a cooperativity between one heteroatom binding the transition metal and a second heteroatom of the ligand performing H atom transfers with one or more reactants .
- methods for reacting alkenes or alkynes with water, alcohols, ammonia or amines comprise contacting the reactants in the presence of a transition metal complex of the invention in an amount effective to facilitate the desired reaction to one or more desired products.
- the contacting occurs at effective reaction conditions.
- terminal alkynes are catalytically converted to aldehydes with high selectivities at or near neutral pH.
- FIG. 1 is an illustration of five compounds comprising a complex of heteroatoms, a heterocycle, and a transition metal.
- FIG. 2 is a graph illustrating the percent conversion of an alkyne to a hydrated form as a function of time for compound 1 of FIG. 1.
- the present invention relates to ligands, transition metal complexes including the ligands, and methods of using the ligands and transition metal complexes .
- Ligands or compounds of the invention may include a first heteroatom which may be located one carbon atom away from a second heteroatom.
- exemplary heteroatoms include nitrogen atoms (N) , oxygen atoms (0) , sulfur atoms (S) phosphorus atoms (P) , arsenic atoms (As) , and antimony atoms (Sb) .
- at least one of the first and second heteroatoms is a nitrogen atom (N) .
- an organic ligand of the invention includes at least one nitrogen heterocycle, for example, a substituted or unsubstituted six- me bered heterocycle.
- a substituted or unsubstituted pyridine rings or groups or imidazole rings or groups may be included in a ligand.
- a ligand of the invention may be neutral in charge.
- the ligand may join two or more heteroatoms separated by at least one intervening atom. At least one of the heteroatoms may bind to a transition metal with another heteroatom substantially free to interact with one or more reactant molecules or intermediates in the catalytic reaction, e.g., water or alkyne.
- Such ligands are conveniently but not only provided by covalently linking one or more heterocyclic ring(s) to one or more heteroatom (s) outside the ring.
- the heteroatom (s) outside the first heterocycle can also be present in a ring structure or not present in a ring structure.
- a ligand covalently links a nitrogen containing heterocycle (e.g., an N heterocycle) with a phosphorous heteroatom outside the heterocyclic ring.
- a ligand may covalently link one or more phenyl, heteroryl, or alkyl groups with a heteroatom, for example, a phosphorous heteroatom, outside the heterocyclic ring.
- a ligand covalently links an N heterocyle and one or more phenyl groups, for example, to two phenyl groups with a phosphorous heteroatom outside the heterocyclic ring.
- a transition metal of the present invention may be partially complexed by at least one of the present organic ligands.
- the transition metal may be a metal selected from Group IB metals, Group IIB metals, Group 11IB metals, Group IVB metals, Group VB metals, Group VIB metals, Group VIIB metals and Group VIIIB metals.
- the transition metal is selected from chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold.
- the transition metal is ruthenium.
- ruthenium is a transition metal useful for alkyne hydration.
- transition metal complex of the present invention is shown by the following structures, wherein "Ri" and “R 2 " are independently- selected from hydrogen or alkyl or aryl .
- Ri and R 2 are t-butyl.
- R 3 may be a hydrogen, alkyl, aryl, halide, water, alcohol, amine, nitrile or derivatives thereof.
- R 3 is a nitrile, for example, an acetonitrile .
- X is a heteroatom which may be for example, a nitrogen atom (N) , an oxygen atom (O) , a sulfur atom (S) , an arsenic atom (As) , or an antimony atom (Sb) .
- X is a phosphorus atom (P) .
- the transition metal shown in the following structures is attached to a ligand or ligands L, which can be selected from compounds such as halide ion(s), nitrile (s), alkene(s), phosphine (s) , carbon monoxide (s), arenes (such as benzene), or tris (pyrazolyl)borate derivatives.
- the ligand L is a derivative of cyclopentadienyl anion, such as C 5 H 5 itself, or substituted derivatives thereof. In an especially useful embodiment, the ligand L is C 5 H 5 .
- the present transition metal complexes preferably are soluble in the liquid medium in which such complexes are present or are used.
- the organic ligands may include one or more substituents, for example, one or more polar substituents and/or non- polar substituents, effective to increase the solubility of the ligand/transition metal complex in a certain liquid medium.
- the present compositions may include one or more other or additional components, such as silver or thallium salts, acids, bases and the like, in an amount effective to interact with or otherwise affect the complex, for example, to activate the complex and/or to enhance the activity of the complex to facilitate a desired chemical reaction.
- the present invention includes within its scope the present ligands and complexes as described herein and any and all substituted counterparts thereof.
- one or more of the hydrogen (H) substituents included in the present ligands can be replaced by another monovalent radical, such as a hydrocarbyl radical.
- Such substituted ligands, as well as the ligands with the hydrogen substituents are included within the scope of the present invention.
- any and all isomers, tautomers, enantiomers, and mixtures thereof of the present ligands are included within the scope of the present invention.
- Examples of monovalent radicals that may be included as substituents in the present ligands, for example, as the R groups include, but not limited to, monovalent hydrocarbon or hydrocarbyl groups, such as alkyl, alkenyl, alkynyl, aryl, alkyl aryl, alkenyl aryl , alkynyl aryl , aryl alkyl , aryl alkenyl , aryl alkynyl and cyclic monovalent hydrocarbon groups; halo such as F, CI, Br and I; NH 2 ; N0 2 ; alkoxy; alkylthio aryloxy; arylthio; alkanoyl; alkanoyloxy; aroyl aroyloxy; acetyl; carbamoyl; alkylamino; dialkylamino arylamino; alkylarylamino; diarylamino; alkanoylamino alkylsulfinyl
- the present invention includes methods for producing a hydrolysis product. Such methods comprise contacting a hydrolysis reactant in the presence of a composition in accordance with the present invention in an amount effective to facilitate the hydrolysis of the hydrolysis reactant to the hydrolysis product. This contacting occurs at effective hydrolysis conditions.
- Such hydrolysis reaction conditions vary widely depending on many factors, such as the reactants and complex being employed, the concentrations of the reactants and complex, the desired product and other factors. However, such reaction conditions are not of critical importance in the present invention and may be selected from conditions conventionally used in similar reactions. Therefore, a detailed presentation of such conditions is not set forth herein.
- the hydrolysis reactant preferably is selected from compounds including amide bonds, nitriles, phosphate esters, and cyanide ions.
- Compounds including amide bonds which may be hydrolyzed in accordance with the present invention include, but are not limited to, formamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N,N- diethylacetamide, propionamide, N-methylpropionamide, N,N-dimeethylpropionamide, N, -diethylpropionamide, butyramide, N-methylbutyramide, N,N- dimethylbutyramide, acrylamide, N-methylacrylamide, N,N-dimethylacrylamide, benzamide, N-methylbenzamide, N,N-dimethylbenzamide, N,N-diethylbenzamide, o-, m- , and p-toluamides and their N-alkylated derivatives, acetanilide, o-, m- , and p-acetotoluidides, 2- acetamidophenol , 3-acetamidophenol, 4-ace
- Nitriles which may be hydrolyzed in accordance with the present invention include, but are not limited to, linear or branched saturated alphatic C 2 - Cis mono- and C 3 -C ⁇ 9 dinitriles and phenyl derivatives thereof, C 4 -C ⁇ 3 saturated alphatic mono- and C 5 -C 14 dinitriles, C 3 -C 18 linear or branched olefinically unsaturated alphatic nitriles, C 6 -C 13 olefinically unsaturated alicyclic nitriles, C 7 -C ⁇ 4 aromatic mono- and dinitriles C 6 -C 8 heterocyclic nitrogen and oxygen mononitriles, C 3 -C cyanoalkanoic amides, C 2 -C 12 saturated aliphatic cyanohydrins or hydroxynitriles, and mixtures of the above-described nitriles.
- Phosphate esters which may be hydrolyzed in accordance with the present invention include, but are not limited to, trialkyl phosphates, triaryl phosphates, dialkyl aryl phosphates, alkyl diaryl phosphates, dialkyl phosphates including DNA and RNA derivatives, diaryl phosphates, alkyl aryl phosphates, alkyl phosphates, aryl phosphates, and analogous phosphonic acid derivatives.
- the present invention includes methods for converting carbon dioxide.
- Such methods comprise contacting carbon dioxide in the presence of a composition in accordance with the present invention in an amount effective to facilitate the conversion of the carbon dioxide to a conversion product.
- the contacting occurs at effective carbon dioxide conversion conditions.
- Such reaction conditions vary widely depending on many factors, such as the complex being employed, concentrations of the carbon dioxide and complex, the desired product and other factors. However, such conditions are not critical in the present invention and may be selected from conditions conventionally utilized in similar carbon dioxide conversion reactions. Therefore, a detailed presentation of such conditions is not set forth here.
- the carbon dioxide conversion product preferably is selected from ureas, carbamates and carbonates.
- ligands of the present invention are capable of efficiently performing this reaction at room temperature, such as at a temperature between about 68 degrees Farenheit and about 77 degrees
- the present ligands can be produced from inexpensive and readily available materials, using chemical synthesis techniques well known in the art.
- the following non-limiting examples illustrate certain aspects of the present invention.
- Hydration rates of an alkyne were examined for five compounds, as shown in FIG. 1. Each compound is identified for convenience as (1) , (2) , (3) , (4) , or (5) .
- Compound 5 has been previously reported by others in the literature (Suzuki, Tokunaga, and Wakatsuki, Org. Lett. 2001, 3, 735-737) .
- Compound 3 was previously described in Angew. Chem. , Int. Ed. Engl. 2001, 40, 3884-3887 disclosed in pending U.S. Patent Application Serial No. 09/785,911, filed February 16, 2001, which is incorporated in its entirety herein by reference.
- Rates are expressed as % conversion per % catalyst per hour
- Catalyst 5 is a very exceptional catalyst previously reported by others in the literature (Suzuki, Tokunaga, and Wakatsuki, Org. Lett . 2001, 3, 735-737) . Note that catalyst 1 hydrates nonyne at least 1000 times faster than catalyst 5, whether the reaction is performed in iso-propanol/H 2 0 (3:1 v/v) or in acetone containing 5 equiv of water.
- catalyst 6 appears to be effective in facilitating the reactions disclosed herein.
- L of catalyst 6 refers to any ligand, such as the ligands disclosed herein, and X " refers to any anion, such as the anions disclosed herein.
- solvent acetone plus 5 equivalents of H 2 0.
- Solvent was i-PrOH-H 2 0 (3:1 v/v) .
- the catalysts are numbered in bold and correspond to catalysts 1 to 5 in Example 3.
- the graph of FIG. 2 shows the hydration of 1- nonyne at room temperature by: 1) 2%
Abstract
Description
Claims
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US46055103P | 2003-04-04 | 2003-04-04 | |
US60/460,551 | 2003-04-04 |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2419929A1 (en) * | 1978-03-14 | 1979-10-12 | Anvar | Catalytic hydration of organic nitrile to amide - using a hydrated metal complex catalyst which is recoverable |
US5637660A (en) * | 1995-04-17 | 1997-06-10 | Lyondell Petrochemical Company | Polymerization of α-olefins with transition metal catalysts based on bidentate ligands containing pyridine or quinoline moiety |
US6380393B1 (en) * | 1999-03-19 | 2002-04-30 | San Diego State University Foundation | Ligands, transition metal complexes and methods of using same |
US6627758B2 (en) * | 1999-03-19 | 2003-09-30 | San Diego State University Foundation | Compositions and methods for hydration of terminal alkynes |
-
2004
- 2004-04-02 US US10/552,249 patent/US20070029528A1/en not_active Abandoned
- 2004-04-02 WO PCT/US2004/010280 patent/WO2004089963A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2419929A1 (en) * | 1978-03-14 | 1979-10-12 | Anvar | Catalytic hydration of organic nitrile to amide - using a hydrated metal complex catalyst which is recoverable |
US5637660A (en) * | 1995-04-17 | 1997-06-10 | Lyondell Petrochemical Company | Polymerization of α-olefins with transition metal catalysts based on bidentate ligands containing pyridine or quinoline moiety |
US6380393B1 (en) * | 1999-03-19 | 2002-04-30 | San Diego State University Foundation | Ligands, transition metal complexes and methods of using same |
US6627758B2 (en) * | 1999-03-19 | 2003-09-30 | San Diego State University Foundation | Compositions and methods for hydration of terminal alkynes |
Non-Patent Citations (1)
Title |
---|
GROTJAHN D.B. ET AL.: "Combined effects of metal and ligand capable of accepting a proton or hydrogen bond catalyze anti-Markovnikov hydration of terminal alkynes", ANGEW. CHEM. INT. ED., vol. 40, no. 20, 2001, pages 3884 - 3887, XP001111839 * |
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